CN107076912A

CN107076912A - The manufacture method of polarizability stacked film or polarization plates

Info

Publication number: CN107076912A
Application number: CN201580053198.2A
Authority: CN
Inventors: 河村真; 河村真一
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2014-10-01
Filing date: 2015-09-25
Publication date: 2017-08-18
Anticipated expiration: 2035-09-25
Also published as: KR20170065531A; CN107076912B; WO2016052331A1; TW201618921A; JPWO2016052331A1

Abstract

The manufacture method of the polarizability stacked film of the present invention contains successively：The aqueous solution of polyvinyl alcohol resin is applied on base material film and the working procedure of coating (S10) of coated film is obtained；Coated film is dried and obtains being formed with base material film the drying process (S20) of the stacked film of polyvinyl alcohol resin layer；Obtain stretching the stretching process (S30) of stacked film to stacked film progress uniaxial tension；Form polarizer layer with being dyed to polyvinyl alcohol resin layer, obtain the dyeing process (S40) of polarizability stacked film, in stretching process (S40), the uniaxial tension is started in the state of the moisture rate of stacked film is more than 0.3 mass %.

Description

The manufacture method of polarizability stacked film or polarization plates

Technical field

The present invention relates to polarizability stacked film or the manufacture method of polarization plates.

Background technology

Polarization plates are widely used as feed element of the polarised light in the display devices such as liquid crystal display device etc..It is inclined as this Vibration plate, use was bonded on the polarizing coating (polarizer layer) formed by polyvinyl alcohol resin in the past is formed by triacetyl cellulose Diaphragm polarization plates, in recent years, with liquid crystal display device opening up into mobile devices such as notebook personal computer, mobile phones Exhibition etc., it is desirable to thin-wall light-weighted.

In the past, after the film to being formed by polyvinyl alcohol resin individually stretching or while stretching, dye is implemented Color processing, crosslinking Treatment and make polarizing coating, and by being layered on diaphragm etc., so as to manufacture polarization plates, still, only It can be thinned to the thickness of the single limit of polarizing coating.On the other hand, it is known that such method：It is arranged on the surface of base material film After the polyvinyl alcohol resin layer of polarizer layer, polyvinyl alcohol resin layer is stretched together with base material film, passed through Dyeing, cross-linking process step and drying process hereafter, polarizer layer is made by polyvinyl alcohol resin layer, so as to by base material The gross thickness of film and polarizer layer is thinned to the limit, and the thickness of polarizer layer (polarizing coating) can be made thinner than ever (for example, ginseng According to patent document 1).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2009-93074 publications

The content of the invention

The invention problem to be solved

It is an object of the present invention in the manufacture method that can manufacture the polarizability stacked film with thin polarizer layer, The method that manufacture possesses the polarizability stacked film of the polarizer layer with excellent optical property is provided, described can manufacture has The manufacture method of the polarizability stacked film of thin polarizer layer is following preparation method：On the surface of base material film, polyvinyl alcohol is set After resin, polyvinyl alcohol resin layer is stretched together with base material film, by dyeing, cross-linking process step and hereafter Drying process, by polyvinyl alcohol resin layer polarizer layer is made, so as to manufacture the polarizability with thin polarizer layer Stacked film.

Means for solving the problems

The present invention includes following proposal.

[1] a kind of manufacture method of polarizability stacked film, it is included successively：Polyvinyl alcohol resin is applied on base material film The aqueous solution and obtain the working procedure of coating of coated film；Above-mentioned coated film is dried and obtains being formed with polyvinyl alcohol on base material film The drying process of the stacked film of resin；Obtain stretching the stretching work of stacked film to above-mentioned stacked film progress uniaxial tension Sequence；Form polarizer layer with being dyed to above-mentioned polyvinyl alcohol resin layer, obtain the dyeing process of polarizability stacked film, And in above-mentioned stretching process, start above-mentioned single shaft drawing in the state of the moisture rate of above-mentioned stacked film is more than 0.3 mass % Stretch.

[2] manufacture method of the polarizability stacked film according to [1], wherein, according to the average moisture of above-mentioned coated film Rate change turns to the mode of 5~65 mass %/minute and carries out above-mentioned drying process.

[3] manufacture method of the polarizability stacked film according to [1] or [2], wherein, contain after above-mentioned drying process There is damping process, the moisture rate of above-mentioned stacked film is adjusted to more than 0.3 mass % by it, after by the damping process damping Above-mentioned stacked film is in the state of its moisture rate is kept for above-mentioned stretching process.

[4] a kind of manufacture method of polarizability stacked film, it is included successively：Polyvinyl alcohol is applied in the one side of base material film It is the aqueous solution of resin and obtains the 1st working procedure of coating of coated film；Above-mentioned coated film is dried and the one side in base material film is obtained On be formed with polyvinyl alcohol resin layer stacked film the 1st drying process；Poly- second is applied on the another side of above-mentioned base material film The aqueous solution of enol system resin and the 2nd working procedure of coating for obtaining two sides coated film；Above-mentioned two sides coated film is dried and obtained The two sides of base material film is formed with the 2nd drying process of the two sides stacked film of polyvinyl alcohol resin layer；To above-mentioned two sides stacked film Carry out uniaxial tension and obtain stretch stacked film stretching process；Formed with being dyed to above-mentioned polyvinyl alcohol resin layer In polarizer layer, the dyeing process for obtaining polarizability stacked film, and above-mentioned stretching process, in the moisture of above-mentioned two sides stacked film Rate be more than 0.5 mass % in the state of start above-mentioned uniaxial tension.

[5] manufacture method of the polarizability stacked film according to [4], wherein, according to dried above-mentioned stacked film Moisture rate carries out above-mentioned 1st drying process for more than 0.3 mass % mode.

[6] manufacture method of the polarizability stacked film according to [4] or [5], wherein, according to being averaged for above-mentioned coated film The average moisture rate change that moisture rate changes with above-mentioned two sides coated film is respectively that the mode of 5~65 mass %/minute is carried out State the 1st drying process and above-mentioned 2nd drying process.

[7] manufacture method of the polarizability stacked film according to any one of [4]~[6], wherein, it is dry the above-mentioned 2nd Contain damping process after drying process, the moisture rate of above-mentioned two sides stacked film is adjusted to more than 0.5 mass % by it, will pass through this Above-mentioned two sides stacked film after damping process damping is in the state of its moisture rate is kept for above-mentioned stretching process.

[8] a kind of manufacture method of polarization plates, it is included：Manufactured by the manufacture method any one of [1]~[7] The process of polarizability stacked film；The surface of the side opposite with above-mentioned base material film of above-mentioned polarizer layer in above-mentioned polarizability stacked film The upper bonding process fitted diaphragm and obtain multilayer film；With peel off above-mentioned base material film from above-mentioned multilayer film and on being possessed State the stripping process of the polarization plates of polarizer layer and said protection film.

Invention effect

In the present invention, the value of the moisture rate by controlling the stacked film for stretching process can obtain possessing with excellent The polarizability stacked film of the polarizer layer of good optical property.

Brief description of the drawings

Fig. 1 is the flow chart of the manufacture method for the polarizability stacked film and polarization plates for showing the 1st embodiment.

Fig. 2 is the flow chart of the manufacture method for the polarizability stacked film and polarization plates for showing the 2nd embodiment.

Embodiment

In this specification, will possess the layer of polyvinyl alcohol resin layer (layer for including polyvinyl alcohol resin) on base material film Stack is referred to as " stacked film ", and the stacked film that the two sides of base material film possesses polyvinyl alcohol resin layer is referred to as " two sides stacked film ".

In addition, the polyvinyl alcohol resin layer with polarizer function is referred to as into " polarizer layer ", will possess on base material film The layered product of polarizer layer is referred to as " polarizability stacked film ", and the layered product that at least one side of polarizer layer possesses diaphragm is referred to as " polarization plates ".Each inscape first to polarizability stacked film and polarization plates is illustrated below, subsequently into these system Make the explanation of method.

[base material film]

As the resin used in base material film, such as transparency, mechanical strength, heat endurance, draftability can be used Etc. excellent thermoplastic resin, appropriate resin can be selected according to their glass transition temperature (Tg) or fusing point (Tm). As the concrete example of thermoplastic resin, it can enumerate：Polyolefin-based resins, polyester based resin, cyclic polyolefin hydrocarbon system resin (drop ice Piece alkene system resin), (methyl) acrylic resin, cellulose esters system resin, polycarbonate-based resin, polyvinyl alcohol resin, It is vinyl acetate system resin, polyarylate system resin, polystyrene resin, polyether sulfone system resin, polysulfones system resin, polyamide-based Resin, polyimides system resins and their mixture, copolymer etc..

Base material film can be the film only formed by a kind of above-mentioned resin or the film for being mixed with two or more resin.Should Base material film can be monofilm or multilayer film.

As polyolefin-based resins, it can enumerate：Polyethylene, polypropylene etc., it easily carries out stable and powerful drawing Stretch, therefore preferably.Furthermore it is also possible to using by making ethene and propylene-ethylene copolymers etc. obtained from propylene copolymerization.Copolymerization The monomer beyond ethene can also be utilized, as monomer that can be with other species of propylene copolymerization, such as alpha-olefin can be enumerated. As alpha-olefin, the alpha-olefin of the alpha-olefin of carbon number more than 4, more preferably carbon number 4~10 is preferably used.If enumerating Carbon number is the concrete example of 4~10 alpha-olefin, for example, 1- butylene, 1- amylenes, 1- hexenes, 1- heptene, 1- octenes, the 1- last of the ten Heavenly stems The straight-chain monoene hydro carbons such as alkene；The branched monoene hydro carbons such as 3-methyl-1-butene, 3- Methyl-1-pentenes, 4-methyl-1-pentene； Vinyl cyclohexane etc..Propylene and can be able to be random copolymer or embedding with the copolymer of other monomers of its copolymerization Section copolymer.The containing ratio of the Component units from other monomers in copolymer can be according to " macromolecule analysis handbook " The method of the record of page 616 of (nineteen ninety-five, the distribution of Kinokuniya bookstore), is asked by carrying out infrared ray (IR) spectroscopic assay .

Above-mentioned central, as the propylene resin for constituting propylene resin film, preferably use propylene homopolymer, third Alkene-ethylene atactic copolymer, propylene -1- butene random copolymers and propylene-ethylene -1- butene random copolymers.

In addition, constitute propylene resin film propylene resin stereospecificity be preferably essentially isotaxy or With vertical structure.Propylene resin to including the propylene resin substantially with isotaxy or syndyotactic stereospecificity For film, its treatability is preferable, and mechanical strength in high temperature environments is excellent.

Polyester based resin is the condensation polymer of the polymer with ester bond, predominantly polybasic carboxylic acid and polyalcohol.It is used Polybasic carboxylic acid is mainly dicarboxylic acids, i.e. 2 yuan carboxylic acid or its lower alkyl esters, such as terephthalic acid (TPA), M-phthalic acid, to benzene two Formic acid dimethyl ester, naphthalene dicarboxylic acids dimethyl ester etc..In addition, used polyalcohol is also mainly glycol, i.e. 2 yuan alcohol, it can enumerate： Propane diols, butanediol, neopentyl glycol, cyclohexanedimethanol etc..As specific resin, it can enumerate：Poly terephthalic acid second Diol ester, polybutylene terephthalate (PBT), PEN, PBN, poly- terephthaldehyde Acid propylene glycol ester, polytrimethylene naphthalate, polycyclohexylene's dimethyl ester, poly- naphthalenedicarboxylic acid cyclohexane dicarboxylates Deng.Hybrid resin, the copolymer of these resins can also suitably be used.

As cyclic polyolefin hydrocarbon system resin, norbornene resin is preferably used.Cyclic polyolefin hydrocarbon system resin is with ring-type The general name for the resin that alkene is polymerized as polymerized unit, can be enumerated for example：Japanese Unexamined Patent Publication 1-240517 publications, day Resin described in this Unexamined Patent 3-14882 publications, Japanese Unexamined Patent Publication 3-122137 publications etc.., can be with as concrete example Enumerate：The alpha-olefins such as the open loop (co) polymer of cyclic olefin, the addition polymers of cyclic olefin, cyclic olefin and ethene, propylene Copolymer (representational be random copolymer), and obtained from being modified with unsaturated carboxylic acid or derivatives thereof to them Graft polymers, and their hydride etc..As the concrete example of cyclic olefin, it can enumerate：Norborneol alkene monomer.

It is commercially available to have various products as cyclic polyolefin hydrocarbon system resin.As concrete example, it can enumerate：TOPAS (registrars Mark) (Topas Advanced Plymers GmbH systems), ARTON (registration mark) (JSR (strain) systems), ZEONOR (registrars Mark) (Japanese auspicious father-in-law's (strain) system), ZEONEX (registration mark) (Japanese auspicious father-in-law's (strain) system), APEL (registration mark) (Mitsui Chemicals (strain) makes).

, can be using arbitrary appropriate (methyl) acrylic resin as (methyl) acrylic resin.It can enumerate For example：The polymethacrylates such as polymethyl methacrylate, methyl methacrylate-(methyl) acrylic copolymer, methyl Methyl acrylate-(methyl) acrylate copolymer, methyl methacrylate-acrylate-(methyl) acrylic copolymer, first Base acrylate-styrene copolymer (MS resins etc.), the polymer with alicyclic alkyl are (for example, methyl methacrylate Ester-(methyl) acrylate ester copolymer, methyl methacrylate-(methyl) acrylic acid norborneol ester copolymer etc.).Can be with It is preferred that enumerating：Polymethyl methacrylate etc. is with the C of methacrylic acid₁-C₆Arrcostab is the polymer of main component.It is used as (first Base) acrylic resin, more preferably use using methyl methacrylate as main component (50~100 weight %, preferably 70~ 100 weight %) methyl methacrylate system resin.

Cellulose esters system resin is the ester of cellulose and aliphatic acid.As the concrete example of such cellulose esters system resin, It can enumerate：Cellulosic triacetate, cellulose diacetate, cellulose tripropionate, cellulose dipropionate etc..In addition, It can also enumerate：Material that substituent with other species etc. is modified a part for these copolymers, hydroxyl etc..Its In, particularly preferred cellulosic triacetate.Cellulosic triacetate is commercially available various products, is obtaining the side of easiness, cost Face is also advantageous.As the example of the commercially available product of cellulosic triacetate, it can enumerate：FUJITAC (registration mark) TD80 (Fuji Photo Film (Ltd.)), FUJITAC (registration mark) TD80UF (Fuji Photo Film (Ltd.)), FUJITAC (registration mark) TD80UZ (Fuji Photo Film (Ltd.)), FUJITAC (registration mark) TD40UZ (Fuji Photo Film (Ltd.)), KC8UX2M (KONICA MINOLTA (strain) makes), KC4UY (KONICA MINOLTA (strain) systems) etc..

Polycarbonate-based resin is the engineering plastics formed by the polymer that monomeric unit is combined via carbonate group, is With higher impact resistance, heat resistance, anti-flammability resin.Further, since makrolon has the high transparency, therefore It is suitable for use in optical applications.Modification etc has been carried out to polymer backbone in order to reduce photoelastic coefficient in optical applications The resin referred to as modified polycarbonate, the copolymerization polycarbonate etc. that improves wavelength dependency also gone out on the market Sell, and can compatibly use.Such polycarbonate resin is widely being sold on the market, can be enumerated for example： Panlite (registration mark) (Supreme Being people is melted into (strain)), Iupilon (registration mark) (Mitsubishi Engineering-Plastics (strain)), SD POLYCA (registration mark) (Sumitomo Tao Shi (strain)), CALIBER (registration mark) (DOW Chemical (strain)) etc..

In base material film, in addition to above-mentioned thermoplastic resin, any appropriate additive can also be added.As such Additive, can be enumerated for example：It is ultra-violet absorber, antioxidant, lubricant, plasticizer, releasing agent, anti-coloring agent, fire-retardant Agent, nucleator, antistatic additive, pigment and colouring agent etc..The content by foregoing illustrative thermoplastic resin in base material film is excellent Elect 50~100 weight %, more preferably more preferably 50~99 weight %, 60~98 weight %, particularly preferably 70 as ~97 weight %.This is because, in the case that the content of the thermoplastic resin in base material film is less than 50 weight %, it is possible to can not Fully show high transparency that thermoplastic resin has originally etc..

The thickness of base material film before stretching can be determined suitably, from the viewpoint of the workability such as intensity, treatability, with And in the present invention from adjustment be formed with base material film polyvinyl alcohol resin layer stacked film moisture rate from the viewpoint of, base The thickness of material film is preferably 50~200 μm, more preferably 70~130 μm.In addition, base material film preferably its fusing point or vitrifying The value of transition temperature is higher than aftermentioned drying process, the temperature range of stretching process.By using such base material film, it can prevent Base material becomes over softness in drying process, stretching process, it is to avoid the film thickness distribution in the face of polyvinyl alcohol resin layer is disliked Change.

, can be in base material film at least formed with polyethenol series in order to improve the adaptation with polyvinyl alcohol resin layer The surface of resin bed side carries out sided corona treatment, corona treatment, flame treatment etc.., can be with addition, in order to improve adaptation The surface for having polyvinyl alcohol resin layer side in the formation of base material film forms the thin layers such as priming coat, bond layer.

(priming coat)

When the surface for having polarizer layer side in the formation of base material film forms priming coat, as priming coat, as long as to base The material of both the stronger closing force of performance to a certain degree of material film and polyvinyl alcohol resin layer, is not just limited particularly It is fixed.The excellent thermoplastic resin such as can use the transparency, heat endurance, draftability.Specifically, it can enumerate：Third Olefin(e) acid system resin, polyvinyl alcohol resin, but it is not limited to these resins.Wherein, the good polyethylene of adaptation is preferably used Alcohol system resin.

As the polyvinyl alcohol resin for being used as priming coat, it can enumerate for example：Polyvinyl alcohol resin and its derivative. As the derivative of polyvinyl alcohol resin, in addition to polyvinyl formal, polyvinyl acetal etc., it can also enumerate：With The unsaturated carboxylic acids such as the alkene such as ethene, propylene, acrylic acid, methacrylic acid, crotonic acid, the Arrcostab of unsaturated carboxylic acid, propylene Acid amides etc. polyvinyl alcohol resin is modified after material.In above-mentioned polyvinyl alcohol resin material, poly- second is preferably used Enol resin.

In order to improve the intensity of priming coat, crosslinking agent can be added in above-mentioned thermoplastic resin.Make an addition to thermoplastic resin The crosslinking agent of fat can use crosslinking agent known to organic system, inorganic system etc..Suitably select to used thermoplastic resin more For suitable crosslinking agent.For example, except epoxy crosslinking agent, isocyanates system crosslinking agent, dialdehyde system crosslinking agent, metal chelating Beyond the low molecule crosslinking agents such as compound system crosslinking agent, methylolated melamine resin, Polyamide Epoxy can also be used Deng macromolecular crosslinking agent etc..When using polyvinyl alcohol resin as thermoplastic resin, polyamide ring is particularly preferably used Oxygen tree fat, methylolated melamine, dialdehyde, metal chelate crosslinMng agent etc. are used as crosslinking agent.

The thickness of priming coat is preferably 0.05~1 μm, more preferably 0.1~0.4 μm.If thinner than 0.05 μm, base The closing force reduction of material film and polyvinyl alcohol resin layer；If than 1 μ m-thick, polarization plates are thickening, so it is not preferred.

[polarizer layer]

Specifically, polarizer layer be make the dichroism pigment upper gas absorption quantity of polyvinyl alcohol resin layer after the stretch and The layer obtained.

As the polyvinyl alcohol resin for constituting polyvinyl alcohol resin layer, it can use to polyvinyl acetate system resin Carry out the resin after saponification.As polyvinyl acetate system resin, except the poly- acetic acid second of the homopolymer as vinyl acetate Outside alkene ester, vinyl acetate and the copolymer of monomer of other energy copolymerization etc. can be also illustrated.As can be common with vinyl acetate Poly- other monomers, can be enumerated for example：Unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class, have Acrylic amide of ammonium etc..

The polyvinyl alcohol resin for constituting polarizer layer (polyvinyl alcohol resin layer) is preferably fully saponified thing.Saponification degree Range preferably from 80.0 moles of %~100.0 mole %, more preferably 90.0 moles %~99.5 mole % scope, and then Most preferably 94.0 moles %~99.0 mole % scope.When saponification degree is less than 80.0 moles of %, exists and be made after polarization plates The unfavorable condition that water resistance, humidity resistance are significantly deteriorated.In addition, the polyethenol series tree using saponification degree more than 99.5 moles of % During fat, dyeing kinetics are significantly slack-off, the polarizability stacked film cannot sometimes with abundant polarization property, produce sometimes in addition such as Lower unfavorable condition：, it is necessary to the dyeing time of common several times in manufacture.

Saponification degree mentioned here is to be represented to make to be used as polyethenol series tree by saponifying process with unit ratio (mole %) The acetate contained in the polyvinyl acetate system resin of the raw material of fat becomes the ratio of hydroxyl, is the numerical value being defined by the formula. It can be obtained with method specified in JIS K 6726 (1994).

Saponification degree (mole %)=(number of hydroxyl) ÷ (number of number+acetate of hydroxyl) × 100

Saponification degree is higher, then it represents that the ratio of hydroxyl is higher, that is, represents to hinder the ratio of the acetate of crystallization lower.

In addition, the polyvinyl alcohol resin used in the present invention can carry out partially modified modified polyvinylalcohol. It can enumerate with for example：The alkene such as ethene, propylene, the unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, unsaturated carboxylic The Arrcostab of acid, the material being modified to polyvinyl alcohol resin such as acrylamide etc..Modified ratio is preferably less than 30 moles of %, more preferably less than 10 moles %.When being performed for more than 30 moles of % modification, it becomes difficult to adsorb dichroism color Element, produces the unfavorable condition of polarization property reduction.

To the average degree of polymerization of polyvinyl alcohol resin, also there is no particular limitation, and preferably 100~10000, more preferably For 1500~8000, and then most preferably 2000~5000.Average degree of polymerization mentioned here is also by according to JIS K The numerical value that the method that 6726 (1994) are determined is tried to achieve.

As the polyvinyl alcohol resin having characteristics that, it can enumerate：Such as PVA124 of (strain) Kuraray (saponification degree：98.0~99.0 moles of %), PVA117 (saponification degrees：98.0~99.0 moles of %), PVA624 (saponification degrees：95.0 ~96.0 moles of %) and PVA617 (saponification degrees：94.5~95.5 moles of %)；Such as Japanese synthetic chemical industry (strain) system AH-26 (saponification degrees：97.0~98.8 moles of %), AH-22 (saponification degrees：97.5~98.5 moles of %), NH-18 (saponification degrees： 98.0~99.0 moles of %) and N-300 (saponification degrees：98.0~99.0 moles of %)；Such as JAPAN VAM＆POVAL CO., LTD. JC-33 (saponification degrees：99.0 moles of more than %), JM-33 (saponification degrees：93.5~95.5 moles of %), JM-26 (saponification Degree：95.5~97.5 moles of %), JP-45 (saponification degrees：86.5~89.5 moles of %), JF-17 (saponification degrees：98.0~99.0 rub Your %), JF-17L (saponification degrees：98.0~99.0 moles of %) and JF-20 (saponification degrees：98.0~99.0 moles of %) etc., it can fit For in the present invention.

The aqueous solution is made in above-mentioned polyvinyl alcohol resin, is coated on base material film and dries, it is poly- so as to be formed Vinyl alcohol resin layer.

Above-mentioned polyvinyl alcohol resin layer is stretched together with base material film, and is orientated, and then gas absorption quantity dichroism Pigment, so as to form polarizer layer.Stretching ratio is preferably more than 5 times, more preferably more than 5 times and less than 17 times.

Polarizer layer thickness (after stretching polyvinyl alcohol resin layer thickness) be less than 10 μm, preferably 7 μm with Under.It is less than 10 μm by making the thickness of polarizer layer, may be constructed slim polarization plates.

As the dichroism pigment used in polarizer layer, it can enumerate for example：Iodine, organic dyestuff etc..As there is engine dyeing Material, for example, can use red BR, red LR, red R, pink LB, rubine (Rubin) BL, purplish red (Bordeaux) GS, sky blue LG, lemon Lemon Huang, indigo plant BR, indigo plant 2R, purplish blue (Navy) RY, green LG, purple LB, purple B, black H, black B, black GSP, Huang 3G, Huang R, orange LR, orange 3R, orangutan Red GL, scarlet KGL, Congo red, brilliant violet BK, Su Pula (Supra) indigo plant G, Su Pula indigo plant GL, Su Pula orange GL, direct sky blue (Direct Sky Blue), chlorazol fast orange d (Direct Fast Orange) S, fast black (Fast Black) etc..These two Color material can be used, or two or more may be used.

[diaphragm]

Diaphragm can without optical function only diaphragm or phase retardation film, brightness improve film this The diaphragm for having optical function concurrently of sample etc..

As the material of diaphragm, it is not particularly limited, for example, can includes comprising cyclic polyolefin resin film, three The cellulose acetate resin film of the resin of acetylcellulose, diacetyl cellulose etc, includes polyethylene terephthalate The polyester based resin film of the resin of ester, PEN, polybutylene terephthalate (PBT) etc, it is polycarbonate-based Resin film, acrylic resin film, the film that polypropylene-based resin film etc. is widely used in the art all the time.

As cyclic polyolefin hydrocarbon system resin, appropriate commercially available product can be applicable, for example, TOPAS (registration mark) (Topas Advanced Polymers GmbH systems), ARTON (registration mark) (JSR (strain) systems), ZEONOR (registration mark) (Japan it is auspicious Father-in-law's (strain) makes), ZEONEX (registration mark) (Japanese auspicious father-in-law's (strain) system), APEL (registration mark) (Mitsui Chemicals (strain) system). When being filmed to such cyclic polyolefin hydrocarbon system resin and forming film, solvent casting method, extrusion by melting can be suitably used Deng known method.Further, it is possible to use Escena (registration mark) (ponding chemical industry (strain) system), SCA40 (ponding chemistry Industrial (strain) system), the cyclic polyolefin hydrocarbon system that is film-made in advance such as ZEONOR (registration mark) film (Japanese auspicious father-in-law's (strain) system) The commercially available product of the film of resin manufacture.

Cyclic polyolefin resin film can be the film by being stretched uniaxially or biaxially., can be with by being stretched Arbitrary phase difference value is assigned to cyclic polyolefin resin film.Can generally deflector roll be rolled out while continuously being drawn Stretch, and utilize heating furnace, the direct of travel towards roller, the direction vertical with the direct of travel or the two directions are drawn Stretch.The temperature of heating furnace be usually near the glass transition temperature of cyclic polyolefin hydrocarbon system resin to glass transition temperature+ 100 DEG C of scope.The multiplying power of stretching is usually 1.1~6 times, preferably 1.1~3.5 times in one direction.

The general surface-active of cyclic polyolefin resin film is poor, thus the preferred pair surface Nian Jie with polarizing coating carry out etc. from Daughter processing, sided corona treatment, ultraviolet treatment with irradiation, flame (flame) processing, saponification process etc. are surface-treated.Wherein, preferably Plasma treatment, the sided corona treatment that can relatively easily implement.

As cellulose acetate resin film, appropriate commercially available product, such as FUJITAC (registration mark) TD80 can be applicable (Fuji Photo Film (Ltd.)), FUJITAC (registration mark) TD80UF (Fuji Photo Film (Ltd.)), FUJITAC (registration mark) TD80UZ (Fuji Photo Film (Ltd.)), FUJITAC (registration mark) TD40UZ (Fuji Photo Film (Ltd.)), KC8UX2M (KONICA MINOLTA (strain) makes), KC4UY (KONICA MINOLTA (strain) systems) etc..

In order to improve viewing angle characteristic, liquid crystal layer etc. can be formed on the surface of cellulose acetate resin film.In addition, in order to Phase difference is assigned, cellulose acetate resin film can be stretched.It is generally fine to acetic acid in order to improve the cementability with polarizing coating Tie up prime system resin film and implement saponification process., can be using the alkali for being immersed in sodium hydroxide, potassium hydroxide etc as saponification process The aqueous solution in method.

The optical layers such as hard conating, antiglare layer, anti-reflection layer can also be formed on the surface of diaphragm as described above.Protecting The method that these optical layers are formed on cuticula surface is not particularly limited, and can use known method.

According to the requirement of slimming, preferably make the thickness of diaphragm thin as much as possible, preferably less than 90 μm, more preferably Less than 50 μm.On the contrary, when excessively thin, intensity decreases, so that processability is deteriorated, therefore preferably more than 5 μm.

[the 1st embodiment]

Fig. 1 is the flow chart of the manufacture method for the polarizability stacked film and polarization plates for showing the 1st embodiment.1st implements The manufacture method of the polarizability stacked film of mode is included successively：

The aqueous solution of polyvinyl alcohol resin is applied in the one side of base material film and the working procedure of coating of coated film is obtained (S10)；

Above-mentioned coated film is dried and obtains being formed with base material film the drying of the stacked film of polyvinyl alcohol resin layer Process (S20)；

Obtain stretching the stretching process (S30) of stacked film to above-mentioned stacked film progress uniaxial tension；With

Above-mentioned polyvinyl alcohol resin layer is dyed and polarizer layer is formed, the dyer of polarizability stacked film is obtained Sequence (S40).

In order to manufacture polarization plates, and then contain successively：

Fit transparent guarantor in above-mentioned polarizability stacked film on the face of the side opposite with above-mentioned base material film of above-mentioned polarizer layer Cuticula, the bonding process (S50) for obtaining multilayer film；With

Above-mentioned base material film is peeled off from above-mentioned multilayer film and obtains possessing above-mentioned polarizer layer and above-mentioned transparent protective film The stripping process (S60) of polarization plates.

The each operation of S10~S60 in Fig. 1 described further below.

[working procedure of coating (S10)]

In the process, the aqueous solution of polyvinyl alcohol resin is applied in the one side of base material film and coated film is obtained.

Material suitable for base material film is as described in the explanation of the inscape of above-mentioned polarizability stacked film.Need explanation It is that base material film preferably uses the base material film that can be stretched within the temperature range of the stretching suitable for polyvinyl alcohol resin.

In working procedure of coating (S10), poly- second obtained from the powder for making polyvinyl alcohol resin preferably is dissolved in into good solvent Enol system resin solution is coated on the surface of base material film to obtain coated film.By via working procedure of coating formation polyvinyl alcohol Resin, can make polyvinyl alcohol resin thinner.Be used as side polyvinyl alcohol resin solution being coated on base material film Method, can suitably be selected using rolling method, die coating method, comma rubbing method, the mould such as bar rubbing method, reverse coating, intaglio plate coating Method known to lip rubbing method, spin-coating method, silk screen print method, jetting type rubbing method, dip coating, spraying process etc..It is preferred that comma is applied Cloth method (scraper for coating), die coating method, die lip rubbing method.

The thickness of the polyvinyl alcohol resin layer of stretching stacked film after stretching in stretching process (S30) is preferably 10 μm Below.Therefore, it is preferably 3~50 μm via the thickness of working procedure of coating (S10) and the resin bed of drying process (S20) formation, more Preferably 5~40 μm.When the thickness of the resin bed is less than 3 μm, excessively thinning after stretching, dyeability significantly deteriorates, therefore not It is preferred that.On the other hand, when the thickness of the resin bed is more than 50 μm, the thickness of the polarizer layer finally given is sometimes more than 10 μ M, thus it is not preferred.

, can be in base material film and polyvinyl alcohol resin in order to improve the adaptation of base material film and polyvinyl alcohol resin layer Priming coat is set between layer.From the viewpoint of adaptation, preferred undercoat is by containing polyvinyl alcohol resin and crosslinking agent etc. Composition formed.Material suitable for priming coat etc. is as described in the explanation of the inscape of above-mentioned polarizability stacked film.

[drying process (S20)]

By the way that the coated film obtained by working procedure of coating (S10) is dried, by the solvent of the aqueous solution of polyvinyl alcohol resin Evaporation, so as to obtain being formed with the stacked film of polyvinyl alcohol resin layer on base material film.

Drying process preferably becomes by the average moisture rate of coated film turns to 5~65 mass %/carried out in the way of minute, more It is preferred that changing 7.5~50 mass %/carried out in the way of minute, further preferably according to coating by the average moisture rate of coated film The mode of average moisture rate change 7.5~30 mass %/minute of film is carried out.The average water of drying process described in this specification The change of point rate refers to the moisture rate (%) of the stacked film at the end of drying the moisture rate (%) of coated film when starting and drying Difference divided by obtained from the time be worth.It should be noted that the computational methods of the moisture rate of coated film or stacked film will later Middle explanation.Average moisture rate changes when being more than 65 mass %/minute, it is necessary to improve drying temperature, and it is therefore possible to produce base material A problem that dissolving of film, polyvinyl alcohol resin change colour, thus it is not preferred.Average moisture rate change be less than 5 mass %/point In the case of clock, productivity ratio is deteriorated, therefore not preferred.

Drying temperature in drying process is such as 50 DEG C~200 DEG C, preferably 60 DEG C~150 DEG C.Drying means, which has, to be blown The various methods such as the method for sending hot blast, the method contacted with hot-rolling, the method heated with IR heaters, can suitably be used. It should be noted that in drying process, for so-called drying temperature, blowing the method for hot blast, setting such as IR heaters In the case of drying equipment Deng drying oven, refer to the ambient temperature in drying oven, set in the drying of the contact-type of hot-rolling etc In the case of standby, refer to the surface temperature of hot-rolling.The layer for being formed with polyvinyl alcohol resin layer is manufactured via process above Folded film.Drying time is such as 2 minutes~20 minutes.

[stretching process (S30)]

In the process, the stacked film obtained by drying process (S20) is stretched.In stretching process (S30), in base material The moisture rate of the stacked film of polyvinyl alcohol resin layer is formed with the one side of film in the state of more than 0.3 mass %, to start Uniaxial tension.It is more than 0.3 mass % by making moisture rate during beginning uniaxial tension, can manufactures and possess with excellent light Learn the polarizability stacked film or polarization plates of the polarizer layer of performance.It should be noted that the adjustment of above-mentioned moisture rate for example can be with Carried out by adjusting the degree of drying in drying process (S20), or progress could be adjusted to by aftermentioned damping process.

Degree of drying in drying process (S20) except becoming outside the pale of civilization according to above-mentioned drying temperature, drying time, always according to The atmosphere formed in the thickness (or weight of per unit area) of polyvinyl alcohol resin overlay on base material film, drying process Moisture concentration, water vapor pressure, humidity for enclosing etc. and change, therefore simple preliminary experiment can be carried out carry out adjusting condition so as to reaching To regulation moisture rate (more than 0.3 mass % and below 3 mass %, preferably more than 0.35 mass % and below 1.8 mass %).Certain In the case of a little, it can also be introduced adjusting to the air of regulation water vapor pressure in drying oven.Dry in this way to regulation The stacked film of moisture rate preferably keep its moisture rate in the state of for stretching process (S30), can also be by described later Damping process is adjusted to after regulation moisture rate for stretching process (S30).

(calculating of the moisture rate of stacked film)

In this specification, the moisture rate of stacked film (or coated film) is the value calculated in the following way.First, from stacking Film (or coated film) is sampled, and obtains the quality (A) of the determination sample, and it is small that the determination sample is then put into 105 DEG C of baking oven into 1 When.Then, the quality (B) from the determination sample after baking oven taking-up is obtained.The moisture rate of stacked film (or coated film) passes through following formula (1) calculate.

The moisture rate of stacked film (or coated film)=(A-B)/A × 100 (%)

(calculating of the moisture rate of polyvinyl alcohol resin layer)

In this specification, the moisture rate of polyvinyl alcohol resin layer is the value calculated in the following way.First, from stacking Film is sampled, and obtains the quality (A) of the determination sample, is then put into the determination sample in 105 DEG C of baking oven 1 hour.Then, ask Go out the quality (B) from the determination sample after baking oven taking-up.And then, polyvinyl alcohol resin layer is removed from the determination sample, is asked Go out the quality (C) of base material film in itself.The moisture rate of polyvinyl alcohol resin layer is calculated by following formula (2).

Moisture rate=(A-B)/(A-C) × 100 (%) of polyvinyl alcohol resin layer

The moisture rate of polyvinyl alcohol resin layer is preferably more than 2.5 mass %.The moisture rate of polyvinyl alcohol resin layer Value in above range, the crackle that produces in the polyvinyl alcohol resin layer after stretching can be suppressed, therefore be preferred.

In stretching process (S30), uniaxial tension is preferably carried out with the stretching ratio more than 5 times and less than 17 times.Further It is preferred that carrying out uniaxial tension with the stretching ratio more than 5 times and less than 8 times.When stretching ratio is less than 5 times, polyethenol series tree Lipid layer orientation is insufficient, therefore as a result, the unfavorable condition that the degree of polarization for producing polarizer layer sometimes can not be improved fully.It is another Aspect, when stretching ratio is more than 17 times, easily occurs the fracture of stacked film during stretching, while the thickness of the stretching stacked film after stretching Degree is thinned to more than the degree of needs, there is processability, the risk of treatability reduction in rear process.In stretching process (S30) Stretch processing be not limited only to the stretching in a stage, multiple stages can also be divided into carry out.Carried out with multiple stages During stretch processing, stretch processing is carried out in the way of the stretching ratio of all stretch processings is total more than 5 times.

In stretching process (S30) in present embodiment, it is possible to implement the vertical stretching carried out to the length direction of stacked film Processing, the horizontal stretch processing stretched to width etc..As vertical stretching mode, drawing process, pressure between roller can be enumerated Contracting drawing process etc., as horizontal stretching mode, can enumerate tenter frame process etc..

In addition, the stretch processing in the present invention preferably uses dry-stretch process to carry out.This is because, by by poly- second Enol resin carries out dry type stretching together with base material film before dyeing process, can will be thinner than ever with high magnification Polyvinyl alcohol resin film (polyvinyl alcohol resin layer) stretching without being broken, can make resulting polarizer layer and then It is thinned polarization plates.

(damping process)

After drying process (S20), there can also be damping process, the moisture rate of stacked film is adjusted to 0.3 matter by it Measure more than % and below 3 mass %, preferably more than 0.35 mass % and below 1.8 mass %.In this case, this will be passed through Stacked film after damping process damping is in the state of more than the mass % of moisture rate 0.3 and below 3 mass % are kept for stretching Process (S30).Damping in damping process can be carried out by the following method：It is adjusted to suitably for example, stacked film is placed in Method in the room of humidity and temperature, the method for making stacked film pass through from the damping stove for being adjusted to suitable humidity and temperature Deng.In damping process, according to the state of stacked film before this, can both increase moisture rate (humidification) can also reduce moisture rate (drying), can not also change moisture rate and form the form that polyvinyl alcohol resin layer homogenizes in itself.

[dyeing process (S40)]

In the process, the polyvinyl alcohol resin layer of stacked film is dyed with dichroism pigment.As dichroism pigment, such as The preceding usable iodine, organic dyestuff.

In the solution containing above-mentioned dichroism pigment, (dyeing is molten for example by will stretch stacked film mass-impregnation for dyeing process Liquid) in carry out.As staining solution, the solution for having dissolved above-mentioned dichroism pigment in a solvent can be used.It is used as dyeing The solvent of solution, can typically use water, can also further add organic solvent having a miscibility with water.It is used as dichroism The concentration of pigment, preferably 0.01~10 weight %, more preferably 0.02~7 weight %, particularly preferably 0.025~5 weight Measure %.

In the case where using iodine as dichroism pigment, from can further improve staining efficiency aspect, Preferably further add iodide.As the iodide, it can enumerate for example：KI, lithium iodide, sodium iodide, zinc iodide, iodine Change aluminium, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide, titanium iodide etc..The adding proportion of these iodide is preferably dye 0.01~20 weight % of color solution.In iodide, KI is preferably added.In the case where adding KI, iodine and iodine The ratio of change potassium is preferably 1: 5~1: 100 scope with weight ratio meter, and more preferably 1: 6~1: 80 scope is particularly preferably 1: 7~1: 70 scope.

Stretch dip time of the stacked film in staining solution to be not particularly limited, it is often preferred that 15 seconds~15 minutes Scope, more preferably 1 minute~3 minutes.In addition, the temperature of staining solution is preferably 10~60 DEG C of scope, more preferably 20 ~40 DEG C of scope.

In dyeing process, crosslinking Treatment can be carried out after dyeing.Crosslinking Treatment is for example by containing crosslinking agent Dipping stretches stacked film to carry out in solution (crosslinker solution).As crosslinking agent, known material can be used.It can arrange Citing is such as：The boron compounds such as boric acid, borax, glyoxal, glutaraldehyde etc..These materials can use one kind, and can also use two More than kind.

As crosslinker solution, the solution for having dissolved crosslinking agent in a solvent can be used.As solvent, it can use for example Water, can also further include organic solvent having a miscibility with water.The concentration of crosslinking agent in crosslinker solution is not limited In this, preferably 1~20 weight % scope, more preferably 6~15 weight %.

Iodide can be added in crosslinker solution.By the addition of iodide, the face of polyvinyl alcohol resin layer can be made Interior polarization characteristic is evenly changed.As iodide, it can enumerate for example：KI, lithium iodide, sodium iodide, zinc iodide, iodate Aluminium, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide, titanium iodide.The content of iodide is 0.05~15 weight %, more Preferably 0.5~8 weight %.

Preferably generally 15 seconds~20 minutes between leaching stain Time of the stretching stacked film in crosslinker solution, more preferably 30 seconds~ 15 minutes.In addition, the temperature of crosslinker solution is preferably in 10~80 DEG C of scope.

Dyeing process (S40) more than, makes polyvinyl alcohol resin layer have the function as polarizer layer, obtains Polarizability stacked film.

[washing procedure]

Then, the washing procedure of washing polarizability stacked film is preferably carried out.It is used as washing procedure, it is possible to implement at water washing Reason.Water washing can generally be carried out by impregnating stretched film in the pure water such as ion exchange water, distilled water.Water washing temperature Degree is usually 3~50 DEG C, preferably 4 DEG C~20 DEG C of scope.Dip time is usually 2~300 seconds, and preferably 3 seconds~240 Second.

Washing procedure can combine the carrying out washing treatment and water washing using iodide solution, can also use suitably The solution of the liquid alcohols such as methanol, ethanol, isopropanol, butanol, propyl alcohol is coordinated.In addition, after washing procedure, can also set makes With the water removal process of niproll, air knife etc..

After washing procedure, preferably polarizability stacked film is dried.More than 60 DEG C of temperature preferably is contained in above-mentioned drying Under drying process, the drying process more preferably at a temperature of more than 70 DEG C.It is of course also possible to different comprising temperature The drying process in multiple stages.In this case, in the drying process in multiple stages, any one drying process is more than 60 DEG C .

In addition to temperature, in order to strengthen drying capacity, the round-robin method of the hot blasts such as air quantity, wind direction can also be carried out excellent Change or IR heaters of progress local heating etc. are set in the lump.Aided in by these, drying efficiency is further improved, helped In the raising of productivity ratio.

The upper limit of drying temperature is preferably less than the temperature of the boiling point of water, preferably shorter than 100 DEG C.And then, preferably 95 DEG C Hereinafter, most preferably less than 90 DEG C.

[bonding process (S50)]

In the process, the face of the side opposite with base material film side of polarizer layer in the polarizability stacked film Jing Guo above-mentioned operation Upper laminating diaphragm, so as to obtain multilayer film.As by the method for polarizer layer and diaphragm laminating, it can enumerate：Via viscous The method that mixture layer, bond layer are fitted to polarizer layer and diaphragm.The material for being suitable as diaphragm is inclined as described above Described in the explanation of the inscape of vibration plate.

(adhesive phase)

The adhesive for constituting adhesive phase is generally comprised with acrylic resin, phenylethylene resin series, silicone-based resin etc. Based on polymer and with the addition of the crosslinking agents such as isocyanate compound, epoxide, aziridine cpd thereto Composition.And then, particulate can also be coordinated in adhesive, light scattering adhesive phase is shown so as to be formed.

The thickness of adhesive phase is preferably 1~40 μm, in the range of processability, the characteristic of durability is not damaged thinly Coating be it is preferred, more preferably 3~25 μm.At 3~25 μm, with good processability, and suppressing polarizing coating It is also preferred thickness in change in size.When adhesive phase is less than 1 μm, cohesive reduction during more than 40 μm, is easily bonded A problem that agent is overflowed.

The method that adhesive phase is formed on diaphragm, polarizer is not particularly limited, can be in protection film surface or polarization Coating includes the solution of each composition by representative of above-mentioned base polymer in piece aspect, dries to form adhesive phase, so The film with distance piece, other species is fitted afterwards, can also be formed on distance piece after adhesive phase, is attached and is layered in diaphragm On face or polarizer aspect.In addition, when forming adhesive phase on diaphragm or polarizer aspect, can be as needed to protection One of film or polarizer aspect and adhesive phase or both carry out closely sealed processing such as sided corona treatment.

(bond layer)

As the bonding agent for constituting bond layer, it can enumerate for example：The polyvinyl alcohol resin aqueous solution, water system are used The water system bonding agent of two-liquid type carbamate system latex bonding agent etc..Wherein, it is preferably water-soluble using polyvinyl alcohol resin Liquid.For the polyvinyl alcohol resin as bonding agent, except the polyvinyl acetate to the homopolymer as vinyl acetate Carry out obtained from saponification process beyond alcotex, also have to vinyl acetate and can be with its copolymerization other monomers Copolymer carry out saponification process obtained from ethenol system copolymer and carry out partially modified to their hydroxyl and obtain Modified polyvinylalcohol based polymer etc..Polyaldehyde, soluble epoxide compound, melamine can be added in water system bonding agent Amine compound, zirconia compound, zinc compound etc. are used as additive.In the case where using such water system bonding agent, Bond layer therefrom is generally significantly thinner than 1 μm, i.e., using common observation by light microscope section, in fact also observe not To the bond layer.

Use the applying method of the film of water system bonding agent to be not particularly limited, can enumerate：In film uniformly Coating or cast bonding agent, are fitted in another overlapping film of coated face and using roller etc., and the method being dried etc..It is logical Often, bonding agent is coated at a temperature of 15~40 DEG C after its preparation, and binding temperature is usually 15~30 DEG C of scope.

Using in the case of water system bonding agent, in order to remove the water contained in water system bonding agent, and fitted film it After be dried.The temperature of drying oven is preferably 30 DEG C~90 DEG C.When less than 30 DEG C, there is bonding plane becomes what is be easily peeled off Tendency.When more than 90 DEG C, it is possible to Yin Re and the optical performance degradation for making polarizer etc..Drying time can be set to 10~ 1000 seconds.

Further 12 can be conserved after drying at a temperature of such as 20~45 DEG C or so of room temperature or the temperature more slightly higher than its ~600 hours or so.Temperature during maintenance be usually set to than it is dry when the temperature that uses it is lower.

In addition, as the bonding agent of non-water system, Photocurable adhesive agent can also be used.As Photocurable adhesive agent, It can enumerate for example：Mixture of photo-curable photoreactive epoxy resin cationic polymerization initiators etc..

As the method that film laminating is carried out with Photocurable adhesive agent, known method can be used, can be enumerated For example：Utilize the tape casting, wire rod rubbing method, gravure coating process, comma rubbing method, doctor blade method, die coating method, dip coating, spraying The coating adhesive on the bonding plane of film such as method, and the method for overlapping 2 films.The tape casting refers to while making as being applied thing 2 films are moved to the incline direction between generally vertical direction, general horizontal direction or both, while flowing down bonding to its surface Agent and the method for deploying it.

After the surface coating adhesive of film, clamped with niproll etc. and 2 films are fitted, be thus bonded.In addition, The method that the layered product is pressurizeed with roller etc. and makes it uniformly sprawl can also be applicable.Now, as the material of roller, it can use Metal, rubber etc..And then, it is also preferred that using by the layered product by between roller and roller, and the side pressurizeed and sprawl it Method.Now, these rollers can be identical material or different materials.Fitted using above-mentioned niproll etc. The thickness before bond layer, dry or solidification afterwards is preferably less than 5 μm and more than 0.01 μm.

In order to improve cementability, corona treatment, sided corona treatment, ultraviolet can be appropriately carried out to the gluing of surfaces of film Treatment with irradiation, flame (flame) processing, saponification process etc. are surface-treated.As saponification process, it can enumerate：Sodium hydroxide, The method impregnated in the aqueous solution of the alkali of potassium hydroxide etc.

In the case where using light-cured resin as bonding agent, by film layer poststack, penetrated by irradiating active-energy Line solidifies Photocurable adhesive agent.The light source of active energy beam is not particularly limited, and preferably has in below wavelength 400nm The active energy beam of luminous distribution, specifically, preferably using low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultra high pressure mercury Lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp etc..

Not having can suitably be determined according to the composition of Photocurable adhesive agent to the photo-irradiation intensity of Photocurable adhesive agent It is particularly limited to, the exposure intensity of the effective wavelength region of the activation to polymerization initiator is preferably 0.1~6000mW/cm².Shining Intensity is penetrated for 0.1mW/cm²During the above, the reaction time will not be long, in 6000mW/cm²When following, seldom occur by from light source spoke The deterioration of the xanthochromia, polarizing coating of the epoxy resin caused by heating during the solidification of the light and heat curability bonding agent of injection.It is right The light irradiation time of Photocurable adhesive agent can be applicable light application time according to the Photocurable adhesive agent to be solidified, without special Limit, preferably according to the accumulated light for making the product representation using above-mentioned exposure intensity and irradiation time as 10~10000mJ/cm²'s Mode is set.Accumulated light to Photocurable adhesive agent is 10mJ/cm²During the above, make its generation sufficient quantity carrys out autohemagglutination The spike of initiator is closed, so as to so that curing reaction is more reliably carried out, in 10000mJ/cm²When following, irradiation time Will not be long, good productivity ratio can be maintained.It should be noted that the thickness of the bond layer after active energy beam irradiation Usually 0.001~5 μm or so, preferably more than 0.01 μm and less than 2 μm, more preferably more than 0.01 μm and 1 μm with Under.

Occur the Photocurable adhesive agent comprising polarizer layer, the film of diaphragm in the irradiation by active energy beam During solidification, preferably in polarization plates such as degree of polarization, transmissivity and the tones and the transparency of diaphragm for not reducing polarizer layer Solidified under conditions of various functions.

It is viscous to be formed using the solution containing solvent in the bonding process (S50) that polarizer layer and diaphragm are fitted In the case of connecing oxidant layer or adhesive phase, implement the drying of multilayer film.Above-mentioned dry main purpose is to implement bond layer or viscous The drying of mixture layer, drying condition etc. is substantially the same with the drying after foregoing washing procedure.Especially with polyethylene In the case that alcohol system resin aqueous solution etc. is to form bond layer, the drying at a temperature of more than 60 DEG C is preferable to carry out.

[stripping process (S60)]

After bonding process (S50), peel off base material film from multilayer film and obtain possessing polarizer layer and guarantor The stripping process (S60) of the polarization plates of cuticula.The method of peeling base film is not particularly limited from multilayer film, can use with The same method of the stripping film stripping process that is carried out in the common polarization plates with adhesive., can be with after bonding process (S50) Directly peeled off, stripping process can also be separately set and peeled off temporarily after wound into rolls immediately.

[other optical layers]

Polarization plates obtained by the present invention can be in the form of being laminated with the polarization plates of other optical layers in actual use To use.In addition, said protection film can also have the function of these optical layers.

As the example of other optical layers, it can enumerate：Transmit certain polarised light and opposite to that property will be shown The reflective polarizing film of polarised light reflection, surface has the film of the anti-dazzle function of the band of concaveconvex shape, belt surface anti-reflective function Film, surface has the reflectance coating of reflection function, has the Transflective film of reflection function and transmission function, compensation film for angular field of view concurrently.

It is used as the reflective polarizing film with transmiting certain polarised light and reflecting the polarised light for showing opposite to that property Suitable commercially available product, can be enumerated for example：DBEF (3M company systems can be obtained from Sumitomo 3M Co., Ltd.), APF (3M Company system, can be obtained from Sumitomo 3M Co., Ltd.).As compensation film for angular field of view, it can enumerate：In substrate surface coating Liquid crystal compounds are simultaneously allowed to the optical compensation films of orientation, the phase retardation film that is formed by polycarbonate-based resin, gathered comprising ring-type The phase retardation film of olefin-based resin.As with substrate surface coating fluid crystalline compound and be allowed to orientation optical compensation films phase When commercially available product, can enumerate：WV films (Fuji Photo Film (Ltd.)), NH films (JX Kuang stones Energy KK system), NV films (JX Kuang stones Energy KK system) etc..In addition, as suitable with the phase retardation film comprising cyclic polyolefin hydrocarbon system resin Commercially available product, can be enumerated：ARTON (registration mark) film (JSR (strain) systems), ESCENA (registration mark) (ponding chemical industry strains Formula commercial firm system), ZEONOR (registration mark) film (Japanese auspicious father-in-law's (strain) system) etc..

[the 2nd embodiment]

Fig. 2 is the flow chart of the manufacture method for the polarizability stacked film and polarization plates for showing the 2nd embodiment.2nd implements The manufacture method of the polarizability stacked film of mode is included successively：

The aqueous solution of polyvinyl alcohol resin is applied in the one side of base material film and the 1st working procedure of coating of coated film is obtained (S11)；

Above-mentioned coated film is dried and obtains being formed with the one side of base material film the stacked film of polyvinyl alcohol resin layer The 1st drying process (S21)；

The 2nd painting of two sides coated film is obtained in the aqueous solution of the another side coating polyvinyl alcohol resin of above-mentioned base material film Apply process (S12)；

Above-mentioned two sides coated film is dried and obtains being formed with the two sides of base material film the two sides of polyvinyl alcohol resin layer 2nd drying process (S22) of stacked film；

Obtain stretching the stretching process (S31) of stacked film to above-mentioned two sides stacked film progress uniaxial tension；With

In order to manufacture polarization plates, and then include successively：

The face laminating of the side opposite with above-mentioned base material film of above-mentioned polarizer layer is transparency protected in above-mentioned polarizability stacked film Film and the bonding process (S50) for obtaining multilayer film；With

In present embodiment, by forming polyvinyl alcohol resin layer on the two sides of base material film, two can be formed simultaneously Polarizer layer.

Below for each operation of the 2nd embodiment in Fig. 2, carried out with the corresponding process of the 1st embodiment in Fig. 1 Contrast, explanation.Carried out it should be noted that the feature being not particularly illustrated is same with the corresponding process of the 1st embodiment.Separately Outside, identical process is with identical symbol and omits the description.

[the 1st working procedure of coating (S11)]

1st working procedure of coating (S11) is the process same with working procedure of coating (S10) in Fig. 1.

[the 1st drying process (S21)]

1st drying process (S21) is more than 0.3 mass % and 3 matter preferably according to the moisture rate of dried stacked film Amount below %, preferably more than 0.35 mass % and below 1.8 mass % mode are carried out.By being set to such moisture rate, In aftermentioned stretching process (S31), moisture rate when easily uniaxial tension is started is adjusted to desired value.1st drying process (S21) the preferred value scope of the average moisture rate change of the coated film in, preferably drying condition etc. is as in the 1st embodiment It is illustrated in drying process (S20).

[the 2nd working procedure of coating (S12)]

2nd working procedure of coating (S12) is in the face of base material film, with being coated with polyvinyl alcohol in the 1st working procedure of coating (S11) It is the process for applying the aqueous solution of polyvinyl alcohol resin on the face of the opposite side in face of the aqueous solution and obtaining two sides coated film.2nd The working procedure of coating (S10) of the coating condition of the aqueous solution of polyvinyl alcohol resin in working procedure of coating (S12) such as the 1st embodiment In it is illustrated.

[the 2nd drying process (S22)]

2nd drying process (S22) is the process same with drying process (S20) in the 1st embodiment.2nd back tender The preferred value scope of the average moisture rate change of coated film, preferably drying condition etc. are also as in the 1st embodiment in sequence (S22) Drying process (S20) in it is illustrated.

[stretching process (S31)]

In the process, the two sides stacked film obtained by the 2nd drying process (S22) is stretched.Stretching process (S31) In, start uniaxial tension in the state of the moisture rate of two sides stacked film is more than 0.5 mass %.By starting uniaxial tension When moisture rate be more than 0.5 mass %, can manufacture possess the polarizer layer with excellent optical property polarizability layer Folded film or polarization plates.It should be noted that the adjustment of above-mentioned moisture rate for example can by adjust the 1st drying process (S21) and Degree of drying in 2nd drying process (S22) is carried out, or can by could be adjusted to carry out in aftermentioned damping process.

Degree of drying in 1st drying process (S21) and the 2nd drying process (S22) is except according in above-mentioned each operation Temperature, the time and become outside the pale of civilization, always according to thickness (or the per unit face for forming polyvinyl alcohol resin overlay on base material film Long-pending weight), moisture concentration, water vapor pressure, the humidity of atmosphere in drying process etc. and change, therefore can carry out simple Preliminary experiment carrys out adjusting condition, thus reached after the 2nd drying process (S22) regulation moisture rate (more than 0.5 mass % and Below 4 mass %, preferably more than 0.6 mass % and below 2.5 mass %).In some cases, can also be by regulation to regulation water The air of vapour pressure is introduced in drying oven.Dried in this way in the 2nd drying process (S22) to the layer for providing moisture rate Folded film, for stretching process (S31), can also be adjusted preferably in the state of its moisture rate is kept by damping process described later For stretching process (S31) after the whole moisture rate for regulation.

(damping process)

After the 2nd drying process (S22), can also further have damping process, it is by the moisture rate of two sides stacked film It is adjusted to more than 0.5 mass % and below 4 mass %, preferably more than 0.6 mass % and below 2.5 mass %.In this case, Can by by the two sides stacked film after above-mentioned damping process damping keep more than the mass % of moisture rate 0.5 and 4 mass % with Under, in the state of preferably more than 0.6 mass % and below 2.5 mass % for stretching process (S31).On in the damping process Damping, be applicable and content is same described in the damping process of the 1st embodiment before this explanation.

Embodiment

[embodiment 1]

Flow chart as shown in Figure 2 is implemented to dyeing process (S40) like that, so as to manufacture two sides polarizability stacked film, enters And implement to stripping process (S60), so as to manufacture polarization plates.

(base material film)

By using multilayer extrusion forming machine coextrusion shape, make 3-tier architecture base material film, the base material film by The propylene-ethylene random copolymer of ethylene unit containing about 5 weight % (make, trade name by Sumitomo Chemical (strain)：Sumitomo Noblen W151, Tm=138 DEG C of fusing point) both sides of resin bed that are formed are configured with and are gathered by the homopolymerization of the homopolymer as propylene Propylene (make, trade name by Sumitomo Chemical (strain)：Sumitomo Noblen FLX80E4, Tm=163 DEG C of fusing point) formed resin Layer.The gross thickness of obtained base material film is 100 μm, and the thickness ratio (FLX80E4/W151/FLX80E4) of each layer is 3/4/3.

(primary coat solution)

By pva powder (Japanese synthetic chemical industry (strain) system, trade name：Z-200, average degree of polymerization 1100 is put down 99.5 moles of % of equal saponification degree) 95 DEG C of hot water is dissolved in, prepare the weight % of concentration 3 aqueous solution.In the obtained aqueous solution, Mixed phase is for crosslinking agent (field ridge chemical industry (strain) system, trade name of the parts by weight of pva powder 2 for 1 parts by weight： Sumirezresin 650), obtain primary coat solution.

(aqueous solution of polyvinyl alcohol resin)

By pva powder ((strain) Kuraray system, trade name：PVA124, average degree of polymerization 2400, mean saponification degree 98.0~99.0 moles of %) 95 DEG C of hot water is dissolved in, prepare the weight % of concentration 8 polyvinyl alcohol water solution.

(the 1st working procedure of coating, the 1st drying process)

One side continuous conveying base material film, while implementing sided corona treatment to its one side, is then existed using path gravure coater The above-mentioned primary coat solution of continuously coating on the face that sided corona treatment is crossed, and dried 3 minutes at 60 DEG C, it is consequently formed 0.2 μm of thickness Priming coat.Then, one side transport membrane is while use the above-mentioned polyvinyl alcohol water solution of comma coater continuously coating on priming coat (the 1st working procedure of coating), and 4 minutes (the 1st drying process) is dried at 90 DEG C, 11.5 μm of thickness is thus formed on priming coat Polyvinyl alcohol resin layer (being set to below " 1PVA layers "), obtains one side stacked film.

(measure of moisture rate)

The moisture rate of one side stacked film to making in the manner described above is measured, and is as a result 0.39 mass %.By this Moisture rate and enter above-mentioned 1st drying process before coated film moisture rate, calculate the rate of drying in the 1st drying process with The change of average moisture rate is calculated as 16.4 mass %/minute.In addition, being carried out to the moisture rate of 1PVA layers of monomer of one side stacked film Determine, be as a result 2.76 mass %.

(the 2nd working procedure of coating, the 2nd drying process)

For the one side stacked film made in the manner described above, there is 1PVA layers of the opposite side in face in the formation with base material film Face on, form 0.2 μm of priming coat as described above, polyvinyl alcohol water solution (the 2nd coating work applied on priming coat Sequence), and 4 minutes (the 2nd drying process) is dried at 90 DEG C, so as to form the polyethenol series of 10.6 μm of thickness on priming coat Resin bed (following, " 2PVA layers "), obtains two sides stacked film.

(measure of moisture rate)

The moisture rate of two sides stacked film to making in the manner described above is measured, and is as a result 0.6 mass %.By the water Divide the moisture rate of rate and the two sides coated film entered before above-mentioned 2nd drying process, calculate the rate of drying in the 2nd drying process 15.9 mass %/minute is calculated as with the change of average moisture rate.In addition, to the water of the independent 1PVA layers of monomer in the stacked film of two sides Point rate and independent 2PVA layers of moisture rate are measured, respectively 4.66 mass % and 3.79 mass %.

(stretching process)

The two sides stacked film that one side continuous conveying is obtained in the manner described above, while the method by being stretched between niproll 5.8 times are stretched along longitudinal direction (film conveying direction) at 160 DEG C of draft temperature, obtains stretching stacked film.In stretching stacked film, 1PVA layers of thickness be changed into 5.7 μm, 2PVA layers of thickness be changed into 5.4 μm.

(dyeing process)

The stretching stacked film that one side continuous conveying is obtained in the manner described above, while being immersed in containing iodine and KI 30 DEG C of staining solution in cause the holdup time be 180 seconds so as to which 1PVA layer and 2PVA layers be dyed after, with 10 DEG C Pure water washes away unnecessary staining solution.Then, it is immersed in the crosslinker solution of 76 DEG C containing boric acid and KI and causes Holdup time is 600 seconds or so to carry out crosslinking Treatment.Then, with 10 DEG C of pure water 4 seconds, and dried at 80 DEG C 300 seconds, so as to obtain polarizability stacked film.

It should be noted that the compounding ratio of staining solution, crosslinker solution is set to：

Water：100 parts by weight

Iodine：0.6 parts by weight

KI：10 parts by weight

Water：100 parts by weight

Boric acid：9.5 parts by weight

KI：5 parts by weight.

(measure of optical property)

For 1PVA layers (the 1st polarizer layers) and 2PVA layers (the 2nd polarizer layer) of obtained polarizability stacked film, To not be that the polarizer layer of measure object is peeled off and removed, so that prepare as measure object comprising polarizer layer and base material film Layered product, acrylic adhesive layer is laminated on the polarizer layer of the layered product and is pasted via the acrylic adhesive layer Close on glass, as evaluation sample.

With the optical characteristics of band integrating sphere spectrophotometer (Japan Spectroscopy Corporation's system, V7100) evaluation of measuring sample. Incident light is set to incident by glass side, the MD transmissivities and TD transmissivities in the range of wavelength 380nm~780nm is obtained, based on formula (3) independent transmissivity, under each wavelength of formula (4) calculating, degree of polarization, and then entered by JIS Z 8,701 2 degree of visuals field (illuminant-C) Row visibility is corrected, and is obtained visibility and is corrected independent transmissivity (Ty) and visibility correction degree of polarization (Py).

In above-mentioned, " MD transmissivities " refers to the direction of the polarised light come out from Glan-Thompson prism with evaluating sample The transmissivity when axis of homology is parallel, is expressed as " MD " in formula (3), formula in (4).In addition, " TD transmissivities " refers to from Glan-Tang Pu The transmissivity when direction for the polarised light that gloomy prism comes out is orthogonal with the axis of homology for evaluating sample, is represented in formula (3), formula (4) For " TD ".

Independent transmissivity (%)=formula of (MD+TD)/2 (3)

Degree of polarization (%)={ (MD-TD)/(MD+TD) }^1/2× 100 formulas (4).

(adhesive solution)

By pva powder ((strain) Kuraray system, trade name：KL-318, average degree of polymerization 1800) it is dissolved in 95 DEG C Hot water, prepares the weight % of concentration 3 polyvinyl alcohol water solution.In the obtained aqueous solution, mixed phase is for pva powder 2 Parts by weight are crosslinking agent (field ridge chemical industry (strain) system, trade name of 1 parts by weight：Sumirezresin650), as bonding agent Solution.

(bonding process)

Polarizability stacked film obtained by one side continuous conveying is above-mentioned, while being applied on the polarizer layer on two sides above-mentioned viscous Connect after agent solution, laminating implements diaphragm (the KONICA MINOLTA of 40 μm of the thickness of saponification process in its applicator surface (strain) makes, trade name：KC4UY, the transparent protective film formed by triacetyl cellulose (TAC)), it is passed between a pair of doubling rollers And crimped, obtain being made up of 1 polarizer layers of KC4UY//priming coat/base material film/priming coat/2 polarizer layers/KC4UY Multilayer film (bonding process).Multilayer film is peeled off between base material film and priming coat, as KC4UY/ 1 polarizer layer/bottoms The two layered products of coating/base material film, priming coat/2 polarizer layers/KC4UY, and then, base material film is peeled off to remove and (peels off work Sequence).Via cyclic polyolefin resin film (the Japanese auspicious father-in-law of 23 μm of bond layer coating thickness on the priming coat of each layered product (strain) makes, trade name：ZF-14), two polarizations being made up of KC4UY/ polarizer layers/priming coat/bond layer/ZF-14 are obtained Plate.There is no the unfavorable condition of fracture in stripping process.

[embodiment 2]

Drying condition in 1st drying process and the 2nd drying process is changed at 90 DEG C 3 minutes, and then, make the 1st dry 1PVA layers of thickness after drying process is changed into 9.2 μm, 2PVA layers of thickness after the 2nd drying process is changed into 9.4 μm, removes Beyond this, polarizability stacked film and polarization plates are made similarly to Example 1.There is no the unfavorable condition hair of fracture in stripping process It is raw.

[embodiment 3]

Drying condition in 1st drying process and the 2nd drying process is changed at 90 DEG C at 2 minutes, then 80 DEG C 1.5 minutes, totally 3.5 minutes, and then, 1PVA layers of thickness after the 1st drying process is changed into 9.3 μm, made the 2nd drying process 2PVA layers of thickness afterwards is changed into 9.2 μm, in addition, and polarizability stacked film and polarization plates are made similarly to Example 1. There is no the unfavorable condition of fracture in stripping process.

[embodiment 4]

Drying condition in 1st drying process and the 2nd drying process is changed at 75 DEG C 2 at 2 minutes, then 80 DEG C Minute, totally 4 minutes, and then, 1PVA layers of thickness after the 1st drying process is changed into 9.0 μm, made after the 2nd drying process 2PVA layers of thickness is changed into 9.1 μm, in addition, and polarizability stacked film and polarization plates are made similarly to Example 1.Peel off There is no the unfavorable condition of fracture in process.

[embodiment 5]

Flow chart as shown in Figure 1 is implemented to dyeing process (S40) like that, so as to manufacture one side polarizability stacked film, enters And implement to stripping process (S60), so as to manufacture polarization plates.Base material film, primary coat solution and polyvinyl alcohol water solution are used and reality Apply the same material of example 1~4.

(the 1st working procedure of coating, the 1st drying process)

One side continuous conveying base material film, while implementing sided corona treatment to its one side, is then existed using path gravure coater The above-mentioned primary coat solution of continuously coating on the face that sided corona treatment is crossed, dries 3 minutes at 60 DEG C, is consequently formed the bottom of 0.2 μm of thickness Coating.Then, one side transport membrane is while use comma coater continuously coating on priming coat above-mentioned polyvinyl alcohol water solution (the 1 working procedure of coating), dry 2 minutes, then dried 1.5 minutes at 80 DEG C at 90 DEG C, add up to and dry (the 1st drying in 3.5 minutes Process), 1PVA layers of 9.2 μm of thickness are thus formed on priming coat, one side stacked film is obtained.

(stretching process)

The one side stacked film that one side continuous conveying is obtained in the manner described above, while the method by being stretched between niproll 5.8 times are stretched along longitudinal direction (film conveying direction) at 160 DEG C of draft temperature, one side stretching stacked film is obtained.Stretch stacked film In, 1PVA layers of thickness is changed into 4.7 μm.

(dyeing process)

The one side obtained in the manner described above stretching stacked film is dyed similarly to Example 1, one side is obtained inclined Shaking property stacked film.

(bonding process)

One side polarizability stacked film obtained by the continuous conveying of one side, while by adhesive solution same as Example 1 (the 1st polarizer layer) is coated on polarizer, and then laminating implements the guarantor of 40 μm of the thickness of saponification process in the applicator surface (KONICA MINOLTA (strain) make cuticula, trade name：KC4UY, the transparent protective film formed by triacetyl cellulose (TAC)), Be passed to be crimped between a pair of doubling rollers, obtain by 1 polarizer layers of KC4UY//priming coat/base material film constitute it is many Tunic (bonding process).

Base material film is peeled off from the base material film in multilayer film and primary coat interlayer and removed, as by the polarizer layers of KC4UY/ the 1st/ The layered product (stripping process) that priming coat is constituted.On the priming coat of obtained layered product, via the μ of bond layer coating thickness 23 M cyclic polyolefin resin film (Japanese auspicious father-in-law's (strain) system, trade name：ZF-14), obtain by 1 polarizer layers of KC4UY//bottom The polarization plates that coating/bond layer/ZF-14 is constituted.There is no the unfavorable condition of fracture in stripping process.

[embodiment 6]

Make the drying condition in the 1st drying process same as Example 4, the thickness for making the PVA layers after the 1st drying process is 9.0 μm, in addition, one side polarizability stacked film and polarization plates are made similarly to Example 5.There is no fracture in stripping process Unfavorable condition occurs.

[comparative example 1]

1PVA layers of thickness after the 1st drying process is set to be changed into 9.0 μm, make 2PVA layers after the 2nd drying process Thickness is changed into 8.9 μm, in addition to the change, and polarizability stacked film and polarization plates are made similarly to Example 1.

[comparative example 2]

1PVA layers of thickness after the 1st drying process is set to be changed into 9.2 μm, make 2PVA layers after the 2nd drying process Thickness is changed into 9.3 μm, in addition to the change, and polarizability stacked film and polarization plates are made similarly to Example 1.

Table 1 is record embodiment 1~6 and drying condition and the table of each measurement result in comparative example 1,2.

[table 1]

As shown in table 1, in comparative example 1,2, the moisture rate for the stacked film of the state of stretching process is less than 0.5 matter Measure the moisture rate after %, and then the 1st drying process and be less than 0.3 mass %.The polarizability stacked film and embodiment 1 of comparative example 1,2 ~6 polarizability stacked film is compared, it is seen that degree correction degree of polarization Py is low value.

In the polarization being made up of KC4UY/ polarizer layers/priming coat/bond layer/ZF-14 made by embodiment 1~6 Acrylic adhesive layer is set on the KC4UY faces of plate and glass is fitted in via the adhesive phase, as evaluation sample, Humidity resistance as shown below is carried out to test and heat-resistance test.As a result, any evaluation sample is in humidity resistance experiment Δ Pys of the Δ Py in 0.001% or so, heat resistant test 0.005% or so, for the level having no problem.To comparing It is that polarization plates made by example 1 and 2 are equally evaluated as a result, Δ Py is big compared with the evaluation sample of embodiment 1~6.

(1) evaluation of humidity resistance

Using extinction photometer (Japanese light splitting (strain) is made, V7100), the ring in 65 DEG C of temperature, relative humidity 90% is determined The Py before visibility correction degree of polarization Py and experiment after the humidity resistance experiment for standing 500 hours under border, obtains both differences Δ Py (Py after Py- experiments before experiment).When determining Py, evaluation is set in the way of incident light irradiation glass surface is made Sample, in addition, after the experiment of above-mentioned humidity resistance, being stood in the environment of 23 DEG C of temperature, relative humidity 55% after about 12 hours Visibility correction degree of polarization Py after determination test.The Δ Py smaller then humidity resistance of absolute value is higher.

(2) evaluation of heat resistance

Carry out the heat-resistance test for standing 500 hours under the dry environment of 85 DEG C of temperature, it is other with above-mentioned humidity resistance Method described in experiment is identical, obtains the visibility correction degree of polarization Py before and after experiment, and obtain both poor Δ Py (experiments Py after preceding Py- experiments).The Δ Py smaller then heat resistance of absolute value is higher.

Claims

1. a kind of manufacture method of polarizability stacked film, it is included successively：

The aqueous solution of polyvinyl alcohol resin is applied on base material film and the working procedure of coating of coated film is obtained；

The coated film is dried and obtains being formed with base material film the drying process of the stacked film of polyvinyl alcohol resin layer；

Obtain stretching the stretching process of stacked film to stacked film progress uniaxial tension；With

Polyvinyl alcohol resin layer is dyed and polarizer layer is formed, the dyeing process of polarizability stacked film is obtained, And

In the stretching process, start the single shaft drawing in the state of the moisture rate of the stacked film is more than 0.3 mass % Stretch.

2. the manufacture method of polarizability stacked film according to claim 1, wherein, according to the average moisture of the coated film Rate change turns to the mode of 5~65 mass %/minute and carries out the drying process.

3. the manufacture method of polarizability stacked film according to claim 1 or 2, wherein, contain after the drying process There is damping process, the moisture rate of the stacked film is adjusted to more than 0.3 mass % by it, after by the damping process damping The stacked film is in the state of its moisture rate is kept for the stretching process.

4. a kind of manufacture method of polarizability stacked film, it is included successively：

The aqueous solution of polyvinyl alcohol resin is applied in the one side of base material film and the 1st working procedure of coating of coated film is obtained；

The coated film is dried and obtains being formed with the 1st of the stacked film of polyvinyl alcohol resin layer in the one side of base material film Drying process；

The aqueous solution of polyvinyl alcohol resin is applied on the another side of the base material film and two sides coated film is obtained the 2nd is applied Process；

The two sides coated film is dried and obtains being formed with the two sides of base material film the two sides stacking of polyvinyl alcohol resin layer 2nd drying process of film；

Obtain stretching the stretching process of stacked film to two sides stacked film progress uniaxial tension；With

In the stretching process, the list is started in the state of the moisture rate of the two sides stacked film is more than 0.5 mass % Axle is stretched.

5. the manufacture method of polarizability stacked film according to claim 4, wherein, according to the dried stacked film Moisture rate carries out the 1st drying process for more than 0.3 mass % mode.

6. the manufacture method of the polarizability stacked film according to claim 4 or 5, wherein, according to being averaged for the coated film The average moisture rate change that moisture rate changes with the two sides coated film is respectively that the mode of 5~65 mass %/minute carries out institute State the 1st drying process and the 2nd drying process.

7. the manufacture method of the polarizability stacked film according to any one of claim 4~6, wherein, it is dry the described 2nd Contain damping process after drying process, the moisture rate of the two sides stacked film is adjusted to more than 0.5 mass % by it, will pass through this The two sides stacked film after damping process damping is in the state of its moisture rate is kept for the stretching process.

8. a kind of manufacture method of polarization plates, it is included：

The process that polarizability stacked film is manufactured by manufacture method according to any one of claims 1 to 7；

On the face of the side opposite with the base material film of the polarizer layer described in the polarizability stacked film fit diaphragm and obtain To the bonding process of multilayer film；With

The polarization plates that the base material film is peeled off from the multilayer film and obtains possessing the polarizer layer and the diaphragm Stripping process.